KR20140060324A - Lithium ion battery - Google Patents

Abstract

A lithium ion battery having a spinel cathode and a non-aqueous electrolyte comprising a fluorinated non-cyclic carboxylic acid ester and / or a fluorinated non-cyclic carbonate solvent is described. The lithium ion battery operates at a high voltage (i.e., up to about 5 V) and has improved cycling performance at high temperatures.

Description

Lithium ion battery {LITHIUM ION BATTERY}

This application claims the benefit of U.S. Provisional Application No. 61 / 530,545, filed September 2, 2011, and U.S. Provisional Application No. 61 / 654,184, filed June 1, 2012, Claiming priority under §119 (e), each of which is incorporated in its entirety by reference in its entirety as part of this application.

The present invention relates to the field of lithium ion batteries. More specifically, the present invention relates to a lithium ion battery comprising a spinel cathode and a non-aqueous electrolyte.

Lithium-ion batteries have been intensively pursued for hybrid electric vehicle (HEV) and plug-in hybrid electric vehicle (PHEV) applications. Both 4 V spinel LiMn ₂ O ₄ and 3.4 V olivine LiFePO ₄ cathodes have attracted much attention in this regard because Mn and Fe are inexpensive and environmentally harmless. Additionally, these cathodes provide higher rate capability and better safety as compared to layered oxide cathodes. However, both the LiMn ₂ O ₄ cathode and the LiFePO ₄ cathode have a limited energy density due to their low capacity or operating voltage. One way to improve energy and power density is to increase the operating voltage. In this regard, the 5 V spinel cathode LiMn _1.5 Ni _0.5 O ₄ has an almost planar operating voltage close to 5 V and a low operating voltage due to the action of Ni ^{2 + / 3 +} and Ni ^{3 + / 4 +} redox couple It has attracted much attention due to its acceptable capacity.

However, the LiMn _1.5 Ni _0.5 O ₄ cathode can be characterized by a sub-cycling performance in conventional carbonate electrolytes, which is due to the fact that during the charge-discharge process three cubic ( the lattice strain during cycling involving the formation of a cubic phase. Other contributors to sub-cycling performance include Li _x Ni _1-x O impurities, and a corrosion reaction between the cathode surface and the carbonate electrolyte at high operating voltages of approximately 5 V.

U.S. Patent No. 6,337,158 (Nakajima) and Liu et al , J. Phys. Chem . C 13: 15073-15079, 2009] to, Mn and Ni in the LiMn _1.5 Ni _0.5 O ₄ in order to improve the cycle characteristics (cyclability), as discussed Li, Al, Mg, Ti, Cr, Fe, Co, Cu in , Zn and Mo have been sought. Cyclic performance improvements in conventional carbonate electrolytes can be achieved at room temperature by partial cation substitution, but high temperature cycling performance remains a problem due to inherent instability of conventional carbonate electrolytes and degradation reactions that accelerate at elevated temperatures have.

U.S. Patent Application Publication No. 2010/0035162 (Chiga) discloses a chain fluorinated carboxylic acid ester represented by the formula CH ₃ COOCH ₂ CH _{3 -x} F _x , wherein x is 2 or 3, and A non-aqueous electrolyte for use in a secondary battery comprising a film-forming chemical that decomposes in the range of +1.0 to 3.0 V based on the equilibrium potential between metal lithium and lithium ion. This electrolyte was used in a secondary battery in which, in various embodiments, a lithium-transition metal oxide cathode with a charge cut-off voltage of 4.2 V was provided.

Despite efforts in the art as described above, there remains a need for a lithium ion battery that operates at a high voltage (i.e., up to about 5 V) and has improved cycling performance at high temperatures.

In one embodiment,

(a) a housing;

(b) an anode and a cathode disposed in the housing and in conductive contact with each other, wherein the cathode is a manganese cathode comprising a lithium-containing manganese composite oxide having a spinel structure as an active material, the lithium-

Li _z Mn _1.5 Ni _x M _y O _4-d

Wherein M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, Zn, Co, Nb, Mo, Ti, Zr, Mg, V and Cu, < y < = 0.12, 0 < = d &lt; = 0.3, 0.00 &lt; z &lt; = 1.1 and z varies with discharge and absorption of lithium ions and electrons during charging and discharging;

(c) a non-aqueous electrolyte composition disposed within the housing and providing an ionic conduction path between the anode and the cathode, wherein the non-aqueous electrolyte composition comprises at least one electrolyte salt and at least one fluorinated non-cyclic carboxylic acid ester and / Or at least one fluorinated acyclic carbonate; And

(d) a lithium ion battery comprising a porous separator between the anode and the cathode is provided herein.

In another embodiment,

(a) a housing;

(b) an anode and a cathode disposed in the housing and in conductive contact with each other, wherein the cathode is a manganese cathode comprising a lithium-containing manganese composite oxide having a spinel structure as an active material, the lithium-

(IB)

Li _z Ni _x M _y Mn _2-xy O _4-d

(Where z is 0.03 to 1.0; z varies depending on the release and absorption of lithium ions and electrons during charging and discharging; x is 0.3 to 0.6; M is Cr, Fe, Co, Li, Al, Ga , Y is from 0.01 to 0.18, and d is from 0 to 0.3; and wherein the composition comprises at least one of Nb, Mo, Ti, Zr, Mg, Zn, V, and Cu;

(c) a non-aqueous electrolyte composition disposed within the housing and providing an ionic conduction path between the anode and the cathode, wherein the non-aqueous electrolyte composition comprises at least one electrolyte salt and at least one fluorinated non-cyclic carboxylic acid ester and / Or at least one fluorinated acyclic carbonate; And

(d) A lithium ion battery including a porous separator between the anode and the cathode is provided herein.

In a further alternative embodiment,

(a) a housing;

(b) an anode and a cathode disposed in the housing and in conductive contact with each other, wherein the cathode comprises a lithium-containing manganese composite oxide having a spinel structure as an active material, and the lithium-

Li Mn _1.5 Ni _x M _y O ₄

(Where M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga and Zn, 0.4? X <0.5 and 0 <y? 0.1);

(c) a non-aqueous electrolyte composition disposed within the housing and providing an ionic conduction path between the anode and the cathode, wherein the non-aqueous electrolyte composition comprises at least one electrolyte salt and at least one fluorinated non-cyclic carboxylic acid ester and / Or at least one fluorinated acyclic carbonate; And

(d) A lithium ion battery including a porous separator between the anode and the cathode is provided herein.

In another alternative embodiment, the fluorinated non-cyclic carboxylic acid ester has the structure:

R ^{1 -} C (O) O - R ²

(Wherein, R ¹ is _{CH 3, CH 2 CH 3,} CH 2 CH 2 CH 3, CH (CH 3) 2, CF 3 CF 2 H, CFH 2, CF 2 R 3, CFHR 3, and CH ₂ R ^f And R ² is independently selected from the group consisting of CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , and CH ₂ R ^f , and R ³ is selected from the group consisting of A C ₁ to C ₃ alkyl group optionally substituted with at least one fluorine, R ^f is a C ₁ to C ₃ alkyl group substituted with at least one fluorine, and further, at least one of R ¹ or R ² is contains at least one fluorine, R ¹ is when the CF ^₂ H, R ₂ can be represented by not a CH _3), and / or,

The fluorinated acyclic carbonates have the following structural formula:

R ^{4 -} OC (O) O - R ⁵

(Wherein, R ⁴ and R ⁵ are independently CH _3, CH ₂ CH _3, CH ₂ CH ₂ CH _3, CH (CH ₃₎ is selected from _2, and CH _2, the group consisting of R ^f, R ^f is at least one by a fluorine in the C ₁ to C ₃ alkyl group substituted by, further, R ⁴ or at least one of R ⁵ can be represented by the box containing at least one fluorine).

In yet another embodiment of the present invention, an electronically powered or assisted device comprising a lithium ion battery as described above is disclosed.

<Figs. 1 to 11>
FIGS. 1 to 11 show the results of the experiments conducted in Examples 1 to 11 in a graph form.

A lithium ion battery, which is a type of rechargeable battery in which lithium ions migrate from the anode to the cathode during discharging and from the cathode to the anode during charging, is disclosed herein. The lithium ion battery disclosed in this specification includes a housing; An anode and a cathode disposed in the housing and in conductive contact with each other; A non-aqueous electrolyte composition providing an ion conduction path between the anode and the cathode; And a porous separator between the anode and the cathode. The lithium ion battery described herein can operate with a cathode at a high voltage (i.e., up to about 5 V for a Li | Li ⁺ reference electrode), so this type of battery is in some cases a "high voltage"Lt; / RTI &gt; This has improved cycling performance at high temperatures compared to other conventional lithium ion batteries.

The lithium ion battery of the present invention includes a cathode which is an electrode of an electrochemical cell where reduction occurs during discharge. In a galvanic cell, for example a battery, the cathode is a more positively charged electrode. In the lithium ion battery of the present invention, the cathode is a manganese cathode including a lithium-containing manganese composite oxide having a spinel structure as a cathode active material. The lithium-containing manganese composite oxide in the cathode as used herein has the formula:

&Lt; RTI ID = 0.0 &

Li _z Mn _1.5 Ni _x M _y O _4-d

Wherein M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, Zn, Co, Nb, Mo, Ti, Zr, Mg, V and Cu, <y? 0.12, 0? d? 0.3, 0.00 <z? 1.1, and z varies depending on the release and absorption of lithium ions and electrons during charging and discharging.

In one embodiment, M in the above formula is Fe; In another embodiment, M in the above formula is Ga; In another embodiment, M in the above formula is Fe and Ga.

In various embodiments of the invention, the values of x and y are: x = 0.38 / y = 0.12, x = 0.39 / y = 0.11, x = 0.40 / y = 0.1, x = 0.41 / y = 0.09, y = 0.08, x = 0.43 / y = 0.07, x = 0.44 / y = 0.06, x = 0.45 / y = 0.05, x = 0.46 / y = 0.04, x = 0.47 / y = 0.03, x = 0.48 / y = 0.02, x = 0.49 / y = 0.01.

In one embodiment, z has a value given by 0.03? Z? 1.1. In another embodiment, z has a value given by 0.03? Z? 1.0.

In one embodiment, M in the formula is at least one metal selected from the group consisting of Al, Cr, Fe, Ga and Zn, 0.4? X <0.5, 0 <y? 0.1, z = 1 d = 0.

It is believed that the lithium cathode material described above is stabilized by the presence of the M component in the compound. The manganese cathode stabilized by another system may also comprise a spinel-layered composite containing a manganese-containing spinel component and a lithium-rich layered structure, as described in U.S. Patent No. 7,303,840.

In an alternative embodiment, the lithium-containing manganese composite oxide in the cathode as used herein has the formula:

(IB)

Li _z Ni _x M _y Mn _2-xy O _4-d

Z is from 0.03 to 1.0, z varies with discharge and absorption of lithium ions and electrons during charging and discharging, x is from 0.3 to 0.6, M is Cr, Fe, Co, Li, Al, Ga, Y is from 0.01 to 0.18, and d is from 0 to 0.3). &Lt; / RTI &gt; In one embodiment, in the above formula, x is 0.38 to 0.48, y is 0.03 to 0.12, and d is 0 to 0.1. In one embodiment, M is at least one of Li, Cr, Fe, Co, and Ga.

The cathode active material as described and used herein may be prepared by methods such as the hydroxide precursor method described by Liu et al . ( J. Phys. Chem . C 13: 15073-15079, 2009) . In such a process, KOH is added to precipitate the hydroxide precursor from a solution containing the required amount of manganese, nickel and other required metal (s) acetate. The resulting precipitate was oven dried, as described in detail in embodiments of the present invention described, in about 800 to about 950 ℃ in oxygen for 3 to 24 hours, and baked together with the amount of LiOH · H ₂ 0 is required. Alternatively, the cathode active material may be prepared using a sol-gel process or a solid phase reaction process as described in U.S. Patent No. 5,738,957 (Amine).

The cathode containing the cathode active material can be produced by reacting an effective amount of a cathode active material (for example, about 70 wt% to about 97 wt%), a polymeric binder such as polyvinylidene difluoride in a suitable solvent such as N-methylpyrrolidone, And conductive carbon to form a paste, and then coating the paste on a current collector such as an aluminum foil and drying to form the cathode.

The lithium ion battery of the present invention further includes an anode which is an electrode of an electrochemical cell where oxidation occurs during discharging. In a galvanic cell, for example a battery, the anode is a more negatively charged electrode. The anode contains an anode active material, which may be any material capable of storing and releasing lithium ions. Examples of suitable anode active materials include, without limitation, lithium alloys, such as lithium-aluminum alloys, lithium-lead alloys, lithium-silicon alloys, lithium-tin alloys, and the like; Carbon materials such as graphite and mesocarbon microbeads (MCMB); Phosphorus-containing materials such as black phosphorus, MnP ₄ and CoP ₃ ; Metal oxides, e.g., SnO _2, SnO ₂ and TiO; And lithium titanates such as Li ₄ Ti ₅ O ₁₂ and LiTi ₂ O ₄ . In one embodiment, the anode active material is lithium titanate or graphite.

The anode can be prepared by a method analogous to that described above for the cathode, in which a binder such as, for example, a vinyl fluoride-based copolymer is dissolved or dispersed in an organic solvent or water and then with the conductive active The paste is obtained by mixing. The paste is coated on a metal foil, preferably aluminum or copper foil, to be used as a current collector. Preferably, heat is used to dry the paste to bond the active material to the current collector. Suitable anode materials and anodes are available from companies such as NEI Inc. (Somerset, NJ) and Farasis Energy Inc. (Hayward, CA).

The lithium ion battery of the present invention further comprises a non-aqueous electrolyte composition which is a chemical composition suitable for use as an electrolyte in a lithium ion battery. The electrolyte composition typically contains at least one non-aqueous solvent and at least one electrolyte salt. The electrolyte salt is an ionic salt that is at least partially soluble in the solvent of the non-aqueous electrolyte composition and is at least partially dissociated into ions in the solvent of the non-aqueous electrolyte composition to form a conductive electrolyte composition. The conductive electrolyte composition allows the cathode and the anode to make ionic conductive contact with one another such that ions, especially lithium ions, move freely between the anode and the cathode and thereby conduct charge through the electrolyte composition between the anode and the cathode.

The solvent in the non-aqueous electrolyte composition of the lithium ion battery of the present invention may contain at least one fluorinated non-cyclic carboxylic acid ester and / or at least one fluorinated non-cyclic carbonate. Suitable fluorinated non-cyclic carboxylic acid esters for use herein as solvents are described by the following structural formula:

&Lt; RTI ID = 0.0 &

R ^{1 -} C (O) O - R ²

Wherein, R ¹ is _{CH 3, CH 2 CH 3,} CH 2 CH 2 CH 3, CH (CH 3) 2, CF 3, CF 2 H, CFH 2, CF 2 R 3, CFHR 3, and CH ₂ R ^f And R ² is independently selected from the group consisting of CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , and CH ₂ R ^f , and R ³ is selected from the group consisting of A C ₁ to C ₃ alkyl group optionally substituted with at least one fluorine, R ^f is a C ₁ to C ₃ alkyl group substituted with at least one fluorine, and further, at least one of R ¹ or R ² is Containing at least one fluorine, and when R ¹ is CF ₂ H, R ² is not CH ₃ .

In some embodiments, R ¹ is _{CH 3, CH 2 CH 3,} CH 2 CH 2 CH 3, CH (CH 3) 2, CF 3, is selected from the CFHR ^3, and CH ₂ group consisting of R ^f, R ² Is independently selected from the group consisting of CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , and CH ₂ R ^f , and R ³ is optionally substituted with at least one fluorine , A C ₁ to C ₃ alkyl group, R ^f is a C ₁ to C ₃ alkyl group substituted with at least one fluorine, and further, at least one of R ¹ or R ² contains at least one fluorine.

In some embodiments, R ¹ is selected from the group consisting of CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , and CH ₂ R ^f and R ² is independently selected from the group consisting of CH ₃ , _{CH 2 CH 3, CH 2 CH} 2 CH 3, CH (CH 3) 2, CH is selected from the group consisting of ₂ R ^f, R ^f is a C ₁ to C ₃ alkyl group substituted with at least one fluorine, more , At least one of R ¹ or R ² contains at least one fluorine.

In another alternative embodiment, fluorine-containing carboxylic acid esters suitable for use herein have the formula:

(IIB)

R ⁸ - C (O) O - R ⁹

(Wherein, R ⁸ and R ⁹ represents an alkyl group independently, R ⁸ and the total of carbon atoms in R ⁹ is 2 numbered to 7, R ⁸ and / or R at least two hydrogen in the ⁹ are replaced by fluorine R ⁸ or R ⁹ any of it can be represented by not containing an FCH ₂ or FCH).

In some embodiments, the fluorinated non-cyclic carboxylic acid ester is:

CH ₃ C (O) OCH ₂ CF ₂ H (2,2-difluoroethyl acetate, CAS No. 1550-44-3),

CH ₃ C (O) OCH ₂ CF ₃ (2,2,2-trifluoroethyl acetate, CAS No. 406-95-1), and

CH ₃ C (O) OCH ₂ CF ₂ CF ₂ H (2,2,3,3-tetrafluoropropylacetate, CAS No. 681-58-3).

In one particular embodiment, the fluorinated non-cyclic carboxylic acid ester solvents include _{CH 3 C (O) OCH 2} CF 2 H.

Fluorinated acyclic carbonates suitable for use as solvents herein may be described by the following structural formula:

(III)

R ^{4 -} OC (O) O - R ⁵

(Wherein, R ⁴ and R ⁵ are independently CH _3, CH ₂ CH _3, CH ₂ CH ₂ CH _3, CH (CH ₃₎ is selected from _2, and CH _2, the group consisting of R ^f, R ^f is at least one by a fluorine in the C ₁ to C ₃ alkyl group substituted by, further, R ⁴ or R ⁵ at least one of which also contains at least one fluorine).

In some embodiments, the fluorinated non-cyclic carbonate solvent comprises:

CH ₃ OC (O) OCH ₂ CF ₂ H (methyl 2,2-difluoroethyl carbonate, CAS No. 916678-13-2),

CH ₃ OC (O) OCH ₂ CF ₃ (methyl 2,2,2-trifluoroethyl carbonate, CAS No. 156783-95-8), and

CH ₃ OC (O) OCH ₂ CF ₂ CF ₂ H (methyl 2,2,3,3-tetrafluoropropyl carbonate, CAS No. 156783-98-1).

In one particular embodiment, the fluorinated non-cyclic carbonate, the solvent is _{CH 3 OC (O) OCH 2} CF 3.

Mixtures of two or more of such fluorinated non-cyclic carboxylic acid ester solvents and / or fluorinated non-cyclic carbonate solvents may also be used.

Fluorinated acyclic carboxylic acid esters and fluorinated acyclic carbonates suitable for use herein may be prepared using known methods. For example, acetyl chloride can be reacted with 2,2-difluoroethanol (with or without a basic catalyst) to form 2,2-difluoroethyl acetate. In addition, 2,2-difluoroethyl acetate and 2,2-difluoroethyl &lt; RTI ID = 0.0 &gt; propyl &lt; / RTI &gt; acetate were prepared using the method described by Wiesenhofer et al. (International Patent Publication No. WO 2009/040367 A1, Can be produced. Similarly, methyl chloroformate can be reacted with 2,2-difluoroethanol to form methyl 2,2-difluoroethyl carbonate. Alternatively, some of these fluorinated solvents may be purchased from companies such as Matrix Scientific (Columbia, SC, USA). For best results, it is desirable to purify the fluorinated non-cyclic carboxylic acid ester and the fluorinated acyclic carbonate to a purity level of at least about 99.9%, more particularly at least about 99.99%. These fluorinated solvents can be purified using distillation methods such as vacuum distillation or spinning band distillation.

The non-aqueous electrolyte composition in the lithium ion battery of the present invention comprises at least one fluorinated non-cyclic carboxylic acid ester and / or fluorinated non-cyclic carbonate as described above, and at least one co-solvent (co -solvent). &lt; / RTI &gt; Examples of suitable co-solvents include, without limitation, ethylene carbonate, propylene carbonate, fluoroethylene carbonate, tetramethylene sulfone and ethyl methyl sulfone. For best results, it is desirable to use a co-solvent having a battery grade or a purity level of at least about 99.9%, more particularly at least about 99.99%. In one embodiment, the co-solvent is ethylene carbonate. In another embodiment, the fluorinated non-cyclic carboxylic acid ester is CH ₃ CO ₂ CH ₂ CF ₂ H and the co-solvent is ethylene carbonate or fluorinated ethylene carbonate.

As described above, the fluorinated non-cyclic carboxylic acid ester and / or the fluorinated non-cyclic carbonate, and the co-solvent may be combined in various ratios depending on the required properties of the electrolyte composition, Solvent mixture can be formed. In one embodiment, the fluorinated non-cyclic carboxylic acid ester and / or the fluorinated non-cyclic carbonate constitutes from about 40% to about 90% by weight of the solvent mixture. In another embodiment, the fluorinated non-cyclic carboxylic acid ester and / or the fluorinated non-cyclic carbonate comprises from about 50% to about 80% by weight of the solvent mixture. In another embodiment, the fluorinated non-cyclic carboxylic acid ester and / or the fluorinated acyclic carbonate comprise from about 60% to about 80% by weight of the solvent mixture. In another embodiment, the fluorinated non-cyclic carboxylic acid ester and / or the fluorinated non-cyclic carbonate comprises from about 65% to about 75% by weight of the solvent mixture. In another embodiment, the fluorinated non-cyclic carboxylic acid ester and / or the fluorinated non-cyclic carbonate constitutes about 70% by weight of the solvent mixture.

In another embodiment, the non-aqueous electrolyte composition comprises a solvent mixture containing a fluorinated non-cyclic carboxylic acid ester CH ₃ CO ₂ CH ₂ CF ₂ H and ethylene carbonate wherein CH ₃ CO ₂ CH ₂ CF ₂ H constitutes about 50% to about 80% by weight of the solvent mixture. In another embodiment, the non-aqueous electrolyte composition contains a solvent mixture of a fluorinated non-cyclic carboxylic acid ester CH ₃ CO ₂ CH ₂ CF ₂ H and ethylene carbonate, wherein CH ₃ CO ₂ CH ₂ CF ₂ H constitutes about 65% to about 75% by weight of the solvent mixture.

The non-aqueous electrolyte composition in the lithium ion battery of the present invention also contains at least one electrolyte salt. Suitable electrolyte salts include, without limitation,

Lithium hexafluorophosphate, Li PF ₃ (CF ₂ CF ₃ ) ₃ ,

Lithium bis (trifluoromethanesulfonyl) imide,

Lithium bis (perfluoroethanesulfonyl) imide,

Lithium (fluorosulfonyl) (nonafluorobutanesulfonyl) imide,

Lithium bis (fluorosulfonyl) imide,

Lithium tetrafluoroborate,

Lithium perchlorate,

Lithium hexafluoroarsenate, lithium hexafluoroarsenate,

Lithium trifluoromethane sulfonate,

Lithium tris (trifluoromethanesulfonyl) methide,

Lithium bis (oxalato) borate,

Lithium difluoro (oxalato) borate,

Li ₂ B ₁₂ F _12-x H _x where x is 0 to 8, and

Lithium fluoride and anion receptors, for example, mixtures of _{B (OC 6 F 5) 3} .

Mixtures of two or more of these or comparable electrolyte salts may also be used. In one embodiment, the electrolyte salt is lithium hexafluorophosphate. The electrolyte salt may be present in the non-aqueous electrolyte composition in an amount of from about 0.2 to about 2.0 M, more particularly from about 0.3 to about 1.5 M, and more particularly from about 0.5 to about 1.2 M.

The non-aqueous electrolyte composition in the lithium ion battery of the present invention may also contain at least one additive which is believed to contribute to film formation on one or both of the electrodes. Suitable such additives include, without limitation,

(Also referred to herein as 4-fluoro-1,3-dioxolan-2-one, CAS No. 114435-02-8) and its halogenated derivatives, C ₁ -C ₃ derivatives And halogenated C ₁ -C ₃ derivatives,

Ethylene sulfates and halogenated derivatives thereof, C ₁ -C ₃ derivatives and halogenated C ₁ -C ₃ derivatives,

Vinyl ethylene carbonate and its halogenated derivatives, C ₁ -C ₃ derivatives and halogenated C ₁ -C ₃ derivatives,

Vinylene carbonate and its halogenated derivatives, C ₁ -C ₃ derivatives and halogenated C ₁ -C ₃ derivatives,

Maleic anhydride and its halogenated derivatives, C ₁ -C ₃ derivatives and halogenated C ₁ -C ₃ derivatives, and

Vinyl acetate.

In one embodiment, the preferred additive is fluoroethylene carbonate.

These additives are generally commercially available; For example, fluoroethylene carbonates are available from companies such as China LangChem INC., Shanghai, China, and MTI Corp., Richmond, CA, USA. It is preferred to purify these additives to a purity level of at least about 99.0%, more particularly at least about 99.9%. Tablets can be made using known methods, as described above. This type of additive, when used, is present in an amount of from about 0.01% to about 5%, more particularly from about 0.1% to about 2%, and more particularly from about 0.5% to about 1.5% by weight of the total electrolyte composition .

The lithium ion battery of the present invention also includes a porous separator between the anode and the cathode. The porous separator serves to prevent a short circuit between the anode and the cathode. The porous separator is typically comprised of a single or multiple sheets of microporous polymer, such as polyethylene, polypropylene, polyamide or polyimide, or combinations thereof. The pore size of the porous separator is large enough to allow ion transport and to provide ionic conductive contact between the anode and the cathode, but it is possible to prevent direct contact of the anode with the cathode, or to prevent dendrites dendrite) or the contact between the anode and the cathode due to particle penetration. Examples of porous separator membranes suitable for use herein are described in U.S. Patent Application No. 12 / 963,927, 2010, which is incorporated herein by reference in its entirety as part of the present application and is disclosed in United States Patent Application Publication No. 2012/0149852 A1, Filed December 9, 1999).

The housing of the lithium ion battery of the present invention may be any suitable container that accommodates the lithium ion battery components described above. Such a container can be made in the shape of a small or large cylinder, a prismatic case or a pouch.

The lithium ion battery of the present invention can be used in a variety of electronic supply or auxiliary devices such as a transport device (including a motor vehicle, an automobile, a truck, a bus or an airplane), a computer, a communication device, a camera, a radio, , For grid storage, or as a power source.

Example

The operation and effect of certain embodiments of the present invention can be more fully appreciated from the series of embodiments described below. It is to be understood that the embodiments on which these embodiments are based are exemplary only and that the selection of these embodiments to illustrate the invention herein is not intended to limit the scope of the present invention to the use of materials, components, reactants, conditions, It is not indicated that the subject matter which is not suitable for use in the application or which is not described in the examples is excluded from the scope of the appended claims and equivalents thereof. The significance of the embodiment is better understood by comparing the result obtained from the embodiment with the result obtained from the predetermined test execution and the test execution is designed to serve as a control experiment and provide the basis for such comparison, This is because different types of solvents have been used in these experimental runs.

The abbreviations used in the examples are as follows: "g" means grams, "mg" means milligrams, "μg" means micrograms, "L" means liter, "mmol" means milliliter, "mol" means mol, "mmol" means millimolar, "M" means molar concentration, "wt%" means weight percent, and " "Means Hertz," mS "means Milli Siemens," mA "means milliampere," mAh / g "means milliampere per gram," V "means bolt , "x C" refers to a constant current capable of fully charging / discharging the cathode at 1 / x time, "SOC " means a charged state," SEI "means a solid electrolyte interface formed on the surface of the electrode material Quot; kPa " means kilo Pascal, "rpm" means the number of revolutions per minute, and "psi " means pounds per square inch.

LiMn _{One .5} Ni _{0 .42} Fe _{0 .08} O ₄ Cathode  Production of active materials

Iron-doped LiMn _1.5 Ni _0.5 O ₄ was synthesized by the hydroxide precursor method described by Liu et al. ( J. Phys. Chem. C 113, 15073-15079, 2009). In this method, 100 mL containing 7.352 g of _{Mn (CH 3 COO) 2 ·} 4H 2 O, 2.090 g of _{Ni (CH 3 COO) 2 ·} 4H 2 O, and 0.278 g of Fe (CH ₃ COO) ₂ The solution was added dropwise to 200 mL of a 3.0 M KOH solution to precipitate the hydroxide precursor. The resulting precipitate was collected by filtration, washed extensively with deionized water, and then dried in an oven to yield 3.591 g of transition metal hydroxide.

Then, the precipitate containing the transition metal hydroxide 1 ℃ / min 900 ℃ was mixed with 0.804 g LiOH · H ₂ O for 12 hours in air at a heating / cooling rate.

The resulting LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ exhibited the same cubic spinel structure as LiMn _1.5 Ni _0.5 O ₄ without impurities when measured by X-ray powder diffraction.

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄  Manufacture of cathode

A cathode active material LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ (2.08 g) prepared as described above, 0.26 g of Denka black (acetylene black available from DENKA Corp., Japan), 2.16 g of 12% by weight of a solution of polyvinylidene difluoride (PVDF) (N-methylpyrrolidone (NMP), Kureha America Inc., KFL # 1120, New York, New York) 2.93 g of NMP were first blended at 2,000 rpm using a planetary centrifugal mixer (THINKY ARE-310, THINKY Corp., Japan), followed by a shear mixer (Wilmington, IKA (registered trademark) Works) to prepare a uniform slurry. The slurry was coated on an aluminum foil using a doctor blade gate and dried at 100 DEG C for 10 to 15 minutes in a convection oven. The resulting electrode was calendered between 102 mm diameter steel rolls with a nip force of 3.63 kN (370 kg) at ambient temperature. The electrode was further dried in a vacuum oven at -85 kPa (-25 in Hg) for 6 hours at 90 &lt; 0 &gt; C.

Preparation of a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate

2,2-Difluoroethyl acetate, obtained from Matrix Scientific (Columbia, SC), was purified twice by spinning band distillation and was purified by gas chromatography using a flame ionization detector When measured, 99.99% purity was obtained. The purified 2,2-difluoroethyl acetate (7.32 g) and 3.10 g of ethylene carbonate (99%, anhydrous, Sigma-Aldrich, Milwaukee, Wisconsin) were mixed together. To a solution of 9.0 mL of the resulting solution was added 1.35 g of lithium hexafluorophosphate (99.99% battery grade, Sigma-Aldrich) and the mixture was shaken for several minutes until all solids dissolved.

Preparation of a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive

4-Fluoro-1,3-dioxolan-2-one obtained from China Langkam-Ink. (Shanghai, China) was purified by vacuum distillation. The purified 4-fluoro-1,3-dioxolan-2-one (0.053 g) was added to 5.30 g of the above non-aqueous electrolyte composition and the mixture was shaken for several minutes.

Methyl 2,2,2-trifluoroethyl carbonate (CH ₃ OC (O) OCH ₂ CF ₃ ) Synthesis of

In a dry-box, chloroformate (232.0 g, Sigma-Aldrich) was added to a solution of 2,2,2-trifluoroethanol (202.0 g, Sigma-Aldrich), pyridine 194.0 g, anhydrous, Sigma-Aldrich) and dichloromethane (1.5 L, anhydrous, EMD Chemicals, Gipston, NJ). The mixture was stirred at room temperature over the weekend. Samples were taken for NMR analysis, in which the conversion of 2,2,2-trifluoroethanol was found to be 100%. The mixture was filtered. The collected solids were washed with dichloromethane and the combined organic liquid filtrate was washed five times with 50 mL portions of 5% HCl. Samples were taken for NMR analysis and pyridine was detected. The organic liquid filtrate was then washed four more times with 25 mL portions of 5% HCl and then pyridine was not detected by NMR. The organic liquid filtrate was washed with brine (50 mL). Dichloromethane was removed from the organic liquid filtrate by rotary evaporation. The crude product (273 g) obtained was dried with molecular sieves and then purified twice by spinning band column distillation. Pure material (101.6 g) was obtained and used for the electrolyte composition.

Preparation of non-aqueous electrolyte compositions comprising methyl 2,2,2-trifluoroethyl carbonate, ethylene carbonate and fluoroethylene carbonate additives

Methyl 2,2,2-trifluoroethyl carbonate (10.0 g) was dried with 4A molecular sieves (1.0 g) over the weekend and then further dried overnight with 4A molecular sieves (1.0 g). The dried methyl 2,2,2-trifluoroethyl carbonate was then filtered through a PTFE (polytetrafluoroethylene) filter plate using a syringe. The dried and filtered methyl 2,2,2-trifluoroethyl carbonate (2.80 g) was mixed with ethylene carbonate (Novolyte, 1.20 g) and the resulting solvent mixture was completely dissolved . To a 2 mL GC vial (oven-dried) was added LiPF ₆ (0.076 g, Novolite, Cleveland, Ohio) followed by 1.0 mL of the solvent mixture. The net weight of the resulting mixture was 1.36 g. The mixture was shaken until all of the solids had dissolved. To this mixture was added 4-fluoro-l, 3-dioxolan-2-one (14 mg, LongChem, Shanghai, China, purified by vacuum distillation). The resulting non-aqueous electrolyte composition was shaken and stored in a dry-box.

Preparation of non-aqueous electrolyte compositions comprising 2,2,2-trifluoroethyl acetate, ethylene carbonate and fluoroethylene carbonate additives

See Shin Quest below grease soil; as a 2,2,2 obtained from (SynQuest Laboratories, Florida Allah Chua material), ethyl acetate _{(CH 3 C (O) OCH} 2 CF 3) by a spinning band distillation column Two times purification, 99.9% purity was obtained as determined by gas chromatography using a flame ionization detector. Purified 2,2,2-trifluoroethyl acetate (10.0 g) was dried with 4A molecular sieves (1.0 g) over the weekend and further dried with 4A molecular sieves (1.0 g) overnight. The dried, purified 2,2,2-trifluoroethyl acetate was then filtered through a PTFE filter plate using a syringe. The filtered material (2.80 g) was mixed with ethylene carbonate (novolol, 1.20 g) and the resulting solvent mixture was shaken until all of the solids had dissolved. To a 2 mL GC vial (oven-dried) was added LiPF ₆ (0.076 g, Novolite, Cleveland, Ohio) followed by 1.0 mL of the solvent mixture. The net weight of the resulting mixture was 1.38 g. The mixture was shaken until all of the solids had dissolved. To this mixture was added 4-fluoro-l, 3-dioxolan-2-one (14 mg, Longchem, Shanghai, China, purified by vacuum distillation). The resulting non-aqueous electrolyte composition was shaken and stored in a dry-box.

Methyl 2,2-difluoroethyl carbonate (CH ₃ OC (O) OCH ₂ CF ₂ H)

Under nitrogen protection, chloroformate (136.1 g, Sigma-Aldrich) was added to a solution of 2,2-difluoroethanol (113.9 g) in an oven-dried 2 L 3 -cylon flask, equipped with overhead stirring and cooling with a water bath. 0 g, Matrix Scientific, Columbia, South Carolina, purified by spinning band column distillation), pyridine (113.9 g, anhydrous, Sigma-Aldrich), and dichloromethane (0.80 L, anhydrous, (TM) &lt; / RTI &gt; in Townsville, CA) over a period of 3 hours via a syringe pump. The resulting mixture was stirred overnight at room temperature. Samples were taken for NMR analysis, in which no 2,2-difluoroethanol was detected. The mixture was filtered and the filtrate was washed with 100 mL of 10% HCl and then twice with 50 mL portions of 10% HCl. Samples were taken for NMR analysis and no pyridine was detected in this assay. Then, the filtrate was washed with 5% Na ₂ CO ₃ a solution of 50 mL, which was then washed with 100 mL of brine. The organic layer was dried with anhydrous MgSO ₄ (50 g) for 2 hours and then dried with molecular sieves (4A, 50 g) overnight. The dried solution was rotary evaporated to remove dichloromethane. The obtained crude product (208 g) was purified by spinning band column distillation. The pure product (101.7 g) was obtained and used for the electrolyte composition.

Preparation of non-aqueous electrolyte compositions comprising methyl 2,2-difluoroethyl carbonate, ethylene carbonate and fluoroethylene carbonate additives

Methyl 2,2-difluoroethyl carbonate (10.0 g) was dried with 4A molecular sieves (1.0 g) overnight and then further dried overnight with 4A molecular sieves (1.0 g). The dried methyl 2,2-difluoroethyl carbonate was then filtered through a PTFE filter plate using a syringe. The filtered material (2.80 g) was mixed with ethylene carbonate (novolol, 1.20 g) and the resulting solvent mixture was shaken until all of the solids had dissolved. To a 2 mL GC vial (oven-dried) was added LiPF ₆ (0.228 g, Nobolite) and then 1.5 mL of the solvent mixture was added. The net weight of the resulting mixture was 2.19 g. The mixture was shaken until all of the solids had dissolved. To 1.0 g of this mixture was added 4-fluoro-1,3-dioxolan-2-one (10 mg, Longchem, Shanghai, China, purified by vacuum distillation). The resulting non-aqueous electrolyte composition was shaken and stored in a dry-box.

Preparation of non-aqueous electrolyte compositions comprising methyl 2,2-difluoroacetate, ethylene carbonate and fluoroethylene carbonate additives

Methyl 2,2-difluoroacetate (HCF ₂ C (O) OCH ₃ ), obtained from Shinquest, is purified twice by spinning band column distillation and is determined by gas chromatography using a flame ionization detector , 99.9% purity was obtained. Purified methyl 2,2-difluoroacetate (10.0 g) was dried with 4A molecular sieves (1.0 g) overnight and then further dried with 4A molecular sieves (1.0 g) overnight. The dried, purified methyl 2,2-difluoroacetate was then filtered through a PTFE filter plate using a syringe. The filtered material (2.80 g) was mixed with ethylene carbonate (novolol, 1.20 g) and the resulting solvent mixture was shaken until all of the solids had dissolved. To a 2 mL GC vial (oven-dried) was added LiPF ₆ (0.228 g, Nobolite) and then 1.5 mL of the solvent mixture was added. The net weight of the resulting mixture was 2.15 g. The mixture was shaken until all of the solids had dissolved. Fluoro-l, 3-dioxolan-2-one (10 mg, Longchem, Shanghai, China, purified by vacuum distillation) was added to a mixture of 1.0 g. The resulting non-aqueous electrolyte composition was shaken and stored in a dry-box.

2,2,3,3-tetrafluoropropylacetate (CH ₃ C (O) OCH ₂ CF ₂ CF ₂ H)

Under nitrogen protection, acetyl chloride (94.2 g, Sigma-Aldrich) was added dropwise to a stirred solution of 2,2,3,3-tetrafluoro-2-methylpropane in an oven dried 0.5 L round bottomed flask equipped with magnetic stirrer and ice / Was slowly added to propanol (132.0 g, 97%, Shinquest) via a syringe pump over a period of 3 hours. The flask was connected via a tube to a 10% NaOH solution trap to capture the generated HCl gas (using a funnel, the NaOH solution was prevented from being sucked into the system again). The mixture was stirred at room temperature overnight. A sample was taken for NMR analysis and 2,2,3,3-tetrafluoropropanol was detected. Acetyl chloride (0.6 g) was added to the mixture and the mixture was stirred at room temperature for 2 hours. NMR analysis indicated that 2,2,3,3-tetrafluoropropanol was not present. The mixture was washed 5 times with 25 mL portions of 10% Na ₂ CO ₃ , then with 25 mL of water, then with 25 mL of brine. The resulting mixture was dried over anhydrous MgSO ₄ (20 g) overnight and then further dried twice with 5 g of 4A molecular sieve. The resulting crude product was purified by spinning band column distillation. Pure material (82.7 g) was obtained and used for the electrolyte composition.

Preparation of a non-aqueous electrolyte composition comprising 2,2,3,3-tetrafluoropropylacetate and ethylene carbonate

2,2,3,3-Tetrafluoropropylacetate (10.0 g) was dried with 4A molecular sieves (1.0 g) overnight and then filtered through a PTFE filter plate using a syringe. The dried and filtered material (2.80 g) was mixed with ethylene carbonate (novolol, 1.20 g) and the resulting solvent mixture was shaken until all of the solids had dissolved. To a 2 mL GC vial (oven-dried) was added LiPF ₆ (0.076 g, Novolite, Cleveland, Ohio) followed by 1.0 mL of the solvent mixture. The net weight of the resulting mixture was 1.42 g. The mixture was shaken until all of the solids had dissolved. The resulting non-aqueous electrolyte composition was filtered through a PTFE filter plate using a syringe and then stored in a dry-box.

Methyl 2,2,3,3-tetrafluoropropyl carbonate (CH ₃ OC (O) OCH ₂ CF ₂ CF ₂ H)

Under nitrogen protection, chloroformate (113.4 g, Sigma-Aldrich) was added to an oven-dried, 2 L, 3-necked flask equipped with overhead stirring and cooling with a water bath, Was added to a solution of propanol (132.0 g, 97%, SynQuest), pyridine (94.9 g, anhydrous, Sigma-Aldrich) and dichloromethane (0.80 L, Lt; / RTI &gt; The resulting mixture was stirred overnight at room temperature. A sample was taken for NMR analysis, and in this analysis, 2,2,3,3-tetrafluoropropanol was not detected. The mixture was filtered and the resulting filtrate was washed with 100 mL of 10% HCl and then twice with 50 mL portions of 10% HCl. NMR analysis showed pyridine to be detected. The mixture was washed again with 50 mL of 10% HCl, and NMR analysis showed no pyridine detected. The mixture was washed with 50 mL of 5% Na ₂ CO ₃ and then with 100 mL of brine. The organic layer was dried with anhydrous MgSO ₄ (50 g) for 2 hours and then dried with molecular sieves (4A, 50 g) overnight. The dried organic layer was rotary evaporated to remove dichloromethane. The resulting crude product was purified by spinning band column distillation. Pure material (96.0 g) was obtained and used for the electrolyte composition.

Preparation of a non-aqueous electrolyte composition comprising methyl 2,2,3,3-tetrafluoropropyl carbonate, and ethylene carbonate

Methyl 2,2,3,3-tetrafluoropropyl carbonate (10.0 g) was dried overnight with 4A molecular sieves (1.0 g). The dried methyl 2,2,3,3-tetrafluoropropyl carbonate was then filtered through a PTFE filter plate using a syringe. The dried and filtered material (2.80 g) was mixed with ethylene carbonate (novolol, 1.20 g) and the resulting solvent mixture was shaken until all of the solids had dissolved. To a 2 mL GC vial (oven-dried) was added LiPF ₆ (0.076 g, Novolite, Cleveland, Ohio) followed by 1.0 mL of the solvent mixture. The net weight of the resulting mixture was 1.43 g. The mixture was shaken until all of the solids had dissolved. The resulting non-aqueous electrolyte composition was filtered through a PTFE filter plate using a syringe and then stored in a dry-box.

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li Production of Half Cell

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ cathode prepared as described above, Celgard TM separator 2325 (Celgard, LLC, Celgard, Charlotte, North Carolina) , Li foil anode (0.75 mm thick) and several drops of the non-aqueous electrolyte composition of interest were placed in a 2032 stainless steel coin battery can (Hohsen Corp., Japan) to form LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li Thereby forming a half-cell.

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O ₁₂  Manufacture of full cell

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ cathode prepared as described above, Celgard TM separator 2325 (Celgard, ELS, Charlotte, NC), Li ₄ Ti ₅ O ₁₂ anode And a few drops of a non-aqueous electrolyte composition of interest were placed in a 2032 stainless steel coin battery can to form LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O ₁₂ hot cells .

Example 1

LiMn &lt; / RTI &gt; having a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate _1.5 Ni _0.42 Fe _0.08 O ₄ / CI room temperature cycling performance of Li battery

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li _half- cell was prepared as described above using the non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate prepared as described above. These LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li halides were cycled between 0.2 C discharge rate (C rate) and 3.5 to 4.95 V at 25 캜. Cycling performance data is shown in FIG. As can be seen from the figure, the LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li reversed cell with a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate has a capacity retention after 100 cycles at room temperature 96%.

Example 2

LiMn with non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate and fluoroethylene carbonate _1.5 Ni _0.42 Fe _0.08 O ₄ / CI room temperature cycling performance of Li battery

Using the non-aqueous electrolyte composition comprising the 2,2-difluoroethyl acetate and fluoro ethylene carbonate additives prepared as described above, LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li Inversion Lt; / RTI &gt; These LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li halides were cycled between 0.2 C discharge rate and 3.5 to 4.95 V at 25 캜.

Cycling performance data is shown in FIG. As can be seen from the figure, a LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li antipode having a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive was subjected to 80 cycles at room temperature The post-capacity retention rate was 98%.

Comparative Example 3

LiMn with standard EC / EMC electrolyte _1.5 Ni _0.42 Fe _0.08 O ₄ / CI room temperature cycling performance of Li battery

Using a standard electrolyte containing ethyl carbonate (EC) / ethyl methyl carbonate (EMC) in a volume ratio of 30:70 and 1 M LiPF ₆ (Novolite, Cleveland, OH, USA) LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li battery. This half-cell was cycled between 0.2 C discharge rate and 3.5 to 4.95 V at 25 캜.

The cycling performance data is shown in Fig. As can be seen from the figure, the capacity maintenance ratio of LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li with a standard EC / EMC electrolyte after 100 cycles at room temperature was 98%.

Example 4

LiMn &lt; / RTI &gt; having a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate _1.5 Ni _0.42 Fe _0.08 O ₄ High cycling performance of Li / Li battery

A non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate was used to prepare a LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li battery as described above. These LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li halides were cycled between 0.5 C discharge rate and 3.5 to 4.95 V at 55 占 폚.

The cycling performance data is shown in FIG. As can be seen from the figure, the LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li reversed cell having a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate had a capacity retention rate of 97% after 100 cycles at 55 ° C .

Example 5

LiMn with non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate and fluoroethylene carbonate _1.5 Ni _0.42 Fe _0.08 O ₄ High cycling performance of Li / Li battery

A non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive was used to prepare a LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li battery as described above. These LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li halides were cycled between 0.5 C discharge rate and 3.5 to 4.95 V at 55 占 폚.

The cycling performance data is shown in Fig. As can be seen from the figure, a LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li reversed cell having a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive was added at 55 The capacity retention rate after the cycle was 99%.

Comparative Example 6

LiMn with standard EC / EMC electrolyte _1.5 Ni _0.42 Fe _0.08 O ₄ High cycling performance of Li / Li battery

Using a standard EC / EMC electrolyte, a LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li battery was prepared as described above. These LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li halides were cycled between 0.5 C discharge rate and 3.5 to 4.95 V at 55 占 폚.

The cycling performance data is shown in Fig. As can be seen, the LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li reversed cell with standard EC / EMC electrolyte had a capacity retention rate of only 39% after 100 cycles at 55 ° C.

Example 7

LiMn with various electrolytes _1.5 Ni _0.42 Fe _0.08 O ₄ / Li Electrochemical Impedance Spectroscopy of Semiconductors

Electrochemical Impedance Spectroscopy (EIS) studies of LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li semiconductors with different electrolytes (see Table 1) were performed at 100% SOC (ie, fully charged) after 100 cycles at 55 ° C . The frequency was in the range of 10 ⁵ Hz to 10 ^-3 Hz. The AC voltage amplitude was 10 mV.

The resulting EIS spectrum is shown in Fig. 7A (Example 1, Half), Fig. 7B (Example 2), and Fig. 7C (Half Example 3), and the results are summarized in Table 1. As can be seen from the data in the table, the SEI resistance Rs and the charge transfer resistance Rct were higher than those of the secondary EC / EMC electrolyte (Comparative Example 3, Having a non-aqueous electrolyte composition comprising ethyl acetate (Example 1) and a non-aqueous electrolyte composition containing 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive (Example 2, half-cell). These results indicate that the non-aqueous electrolyte composition containing the fluorinated component inhibited SEI expression and significantly improved surface charge mobility at elevated temperature (55 &lt; 0 &gt; C).

Example 8

LiMn with non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate and fluoroethylene carbonate _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O ₁₂  High temperature cycling performance of on-cell

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O ₁₂ hot cells as described above were prepared using a non-aqueous electrolyte composition comprising 2,2-difluoroethyl acetate and a fluoroethylene carbonate additive. Respectively. This LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O ₁₂ hot cell was cycled between 0.5 C discharge rate and 1.95 to 3.4 V at 55 ° C.

The cycling performance is shown in FIG. As can be seen from the figure, the LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O ₁₂ battery had a capacity retention rate of 94.8% after 100 cycles at 55 ° C.

Comparative Example 9

LiMn with standard EC / EMC electrolyte _1.5 Ni _0.5 O ₄ / Li ₄ Ti ₅ O ₁₂  High temperature cycling performance of on-cell

LiMn _1.5 Ni _0.5 O ₄ / Li ₄ Ti ₅ O ₁₂ hot cells were prepared as described above using standard ethyl carbonate (EC) / ethyl methyl carbonate (EMC) electrolytes. These LiMn _1.5 Ni _0.5 O ₄ / Li ₄ Ti ₅ O ₁₂ batteries were cycled between 0.5 C discharge rate and 1.95 to 3.4 V at 55 ° C.

The cycling performance is shown in Fig. As can be seen in the figure, for the LiMn _1.5 Ni _0.5 O ₄ / Li ₄ Ti ₅ O ₁₂ on cell with a standard electrolyte, only 61.9% capacity retention was observed after 100 cycles at 55 ° C.

Example 10

CH ₃ OCO ₂ CH ₂ CF ₂ LiMn with a non-aqueous electrolyte composition comprising H: EC (70:30) and fluoroethylene carbonate _1.5 Ni _0.42 Fe _0.08 O ₄ High cycling performance of Li / Li battery

Using a non-aqueous electrolyte composition comprising CH ₃ OCO ₂ CH ₂ CF ₂ H: EC (70:30) and a fluoroethylene carbonate additive (1%), LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li &lt; / _RTI &gt; This LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li halide was cycled between 55 and 3.5 V to 4.95 V at 60 mA / g.

The cycling performance data is shown in Fig. The capacity retention after 100 cycles at 55 캜 was as high as 98%, indicating that the cathode / fluorinated electrolyte combination had very good hot cycling performance.

Comparative Example 11

CF ₂ HCO ₂ CH ₃ : EC (70:30) and a non-aqueous electrolyte composition comprising fluoroethylene carbonate _1.5 Ni _0.42 Fe _0.08 O ₄ High cycling performance of Li / Li battery

Using a non-aqueous electrolyte composition comprising CF ₂ HCO ₂ CH ₃ : EC (70:30) and fluoroethylene carbonate additive (1%), LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li A half-cell was fabricated. This LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li halide was cycled between 55 and 3.5 V to 4.95 V at 60 mA / g.

Cycling performance data is shown in Fig. The capacity retention after 100 cycles at 55 占 폚 was only 23%, indicating that this cathode / fluorinated electrolyte combination has very poor high temperature cycling performance.

Examples 12 to 22

LiMn &lt; / RTI &gt; having a non-aqueous electrolyte composition comprising a variety of fluorinated solvents _1.5 Ni _0.5 O ₄ / Li ₄ Ti ₅ O ₁₂  High temperature cycling performance of on-cell

The following description of the preparation is typically used in the following examples.

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄  Preparation of cathode active material

Iron-doped LiMn _1.5 Ni _0.5 O ₄ was synthesized by the hydroxide precursor method described by Liu et al. ( J. Phys. Chem. C 113, 15073-15079, 2009). In this preparation, 401 g of manganese (II) acetate tetrahydrate (Sigma-Aldrich), 115 g of nickel (II) acetate tetrahydrate (Sigma-Aldrich) and 15.2 g of anhydrous iron (II) acetate (Alfa Aesar, Hill, Mass.) Were weighed on a balance and subsequently dissolved in 5 L of deionized water to prepare an acetate solution. In a 30 L reactor, KOH pellets were dissolved in 10 L of deionized water to form a 3.0 M solution. The acetate solution was transferred to the addition funnel and quickly dripped into the stirred reactor to precipitate the mixed hydroxide material. Once all of the 5 L of acetate solution had been added to the reactor, stirring was continued for 1 hour. Stirring was then stopped and the hydroxide precipitate was allowed to settle overnight. After submerging, the liquid was removed from the reactor and 15 L fresh deionized water was added. The contents of the reactor were agitated, resuspended, and the liquid removed. The rinsing process was repeated. The precipitate was then transferred to two (evenly divided) rough glass frit filtration funnels covered with Dacron (R) paper. The collected solids were rinsed with deionized water until the filtrate pH reached 6.0 (pH of the deionized rinse water) and an additional 20 L of deionized water was added to each filter cake. Finally, the cake was dried in a vacuum oven at 120 &lt; 0 &gt; C overnight. The yield at this point was typically 80-90%.

The hydroxide precipitate filter cake was then pulverized and mixed with lithium carbonate. This step was performed in a 60 g batch using a Fritsch Pulverisette automated pestle and an automated mortar and pestle (Fritsch USA, Goshen, New York) . For each batch, the hydroxide precipitate was weighed and then ground alone in a pull burry set for 5 minutes. Subsequently, a stoichiometric amount plus a slight excess of lithium carbonate was added to the system. For 53 g of hydroxide, 11.2 g of lithium carbonate was added. Every 10 to 15 minutes, the milling was continued for a total of 60 minutes, scraping off the material from the surface of the pestle and mulch bowl with a sharp metal spatulaer. If the material forms agglomerates due to moisture, it is sieved through a 40 mesh screen once during milling and then subsequently milled again.

The pulverized material was calcined in a shallow rectangular alumina tray in an air box furnace. The trays were 158 mm x 69 mm in size, each containing about 60 g of material. The firing procedure consisted of increasing the temperature from room temperature to 900 ° C in 15 hours, maintaining the temperature at 900 ° C for 12 hours, and then cooling to room temperature in 15 hours.

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄  Manufacture of cathode

The cathode was prepared using the LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ spinel cathode material prepared as described above. A binder was obtained as a 12% solution of polyvinylidene fluoride in NMP (KFL # 1120, Kureha America Corp, New York, NY). (0.260 g, acetylene black, Denka Corporation, New York, NY, uncompressed), 3.88 g NMP, and PVDF solution (2.16 g) were combined in a 15 mL vial having a fluoropolymer cap and Sinky ARE And centrifuged three times for 3 minutes each at 2,000 rpm using a -310 centrifugal separator (ThinkK Corporation, Japan). The cathode material (2.08 g) was milled for approximately 1 hour using a mortar and mortar. Then, the cathode material and 0.70 g of NMP were added to the vial and the mixture was centrifuged again three times for 1 minute each at 2000 rpm to form a cathode paste. The total weight of the paste was 9.08 g (28.6% solids). The vials were mounted in an ice bath and placed at 6500 rpm using a rotor-stator (model PT 10-35 GT, 7.5 mm diameter stator, Kinematicia, Bohemia, NY) Lt; / RTI &gt; and then homogenized twice more at 9500 rpm for 15 minutes each. During each of the four homogenization periods, the homogenizer was moved to another location in the paste vial. Using a doctor blade with a gate height of 0.25 mm, the paste was cast on an untreated aluminum foil and dried at 100 DEG C for 15 minutes in a vacuum oven. The resulting 50 mm wide cathode was placed on a 125 micron thick brass sheet and two 37 mm and 38 mm wide brim shim strips were placed on both sides of the cathode to define the gap thickness in the calender It helped me to adjust. The cathode and shims were covered with a second brass sheet of 125 μm thickness and the assembly was passed twice through the calender at a nip force of 5.49 and then 6.67 kN (560 and then 680 kg) using a 100 mm diameter steel roll at ambient temperature . The average cathode thickness was reduced from 67 μm to 45 μm before calendering. Additional cathodes were prepared in a similar manner, except that the gate height of the doctor blade was increased to 0.29 mm and the cathode was dried.

Preparation of Lithium Titanate Anode

PVDF solution (3.00 g, 13% in NMP, KFL # 9130, Kureha American Corporation, New York, New York, USA), and 6.03 (0.39 g acetylene black, Denka Corporation, New York, g of NMP were combined and centrifuged three times at 2000 rpm for 60 seconds each. Li ₃ Ti ₅ O ₁₂ powder (3.12 g, Nanomyte BE-10, NEI Corporation, Somerset, NJ) and an additional 1.10 g NMP were added to the carbon black and PVDF mixture And the resulting paste was centrifuged three times at 2000 rpm for 60 seconds each. The vials were mounted in an ice bath and homogenized twice for 15 minutes each at 6500 rpm using a rotor-stator and then homogenized twice more at 9500 rpm for 15 minutes each. The paste was poured into a bowl and manually pulverized manually using a mortar to remove the aggregate. Then, using a doctor blade having a gate height of 0.29 mm, the paste was cast on an untreated aluminum foil having a thickness of 25 탆. The paste was dried at 100 占 폚 for 15 minutes in a convection oven (model FDL-115, Binder Inc., Great River, NY). The thickness of the anode was 71 μm. The resulting 50 mm wide anode was calendered in a manner similar to the cathode described above. The average anode thickness was reduced from 71 μm before calendering to 53 μm after calendering.

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O ₁₂  Production of on-cell

A non-aqueous electrolyte lithium-ion CR2032 coin cell was prepared for electrochemical evaluation. The circular anode and the cathode were punched out and placed in a heater of an antechamber of a glove box and further dried overnight at 100 ° C under vacuum and placed in an argon glove box (Vacuum Atmospheres, Hawthorn, CA, USA) ), Equipped with a HE-493 purifier). The electrode diameter was a 14.1 mm cathode used with a 16.0 mm anode, or a 10.1 mm cathode used with a 12.3 mm anode. The ratio of lithium titanate weight to Fe-LNMO weight was greater than 1.0 for all cells, so that all batteries were cathode limited. Coin battery parts (cases, separators, wave springs, gaskets, and lids) and coin battery crimpers were obtained from Hohsen Corp (Osaka, Japan). The separator used was a 25 micron thick microporous polyolefin separator (CG2325, Celgard, Charlotte, NC). The electrolytes used in each example are given in Table 1.

LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O ₁₂  High-temperature cycling of on-cell

Using a commercial battery tester (Series 4000, Maccor, Tulsa, Okla.) At 55 ° C using a voltage limit of 1.9 and 3.4 V, LiMn _1.5 Ni _0.42 Fe _0.08 O ₄ / Li ₄ Ti ₅ O _{12 The} whole battery was cycled. The first 29 cycles were performed using constant current charging and discharging at a rate of 60 mA per gram of Fe-LNMO. In the 30th cycle, the ratio was reduced to 24 mA / g. This set of 30 cycles (29 + 1) was repeated 10 times for a total of 300 cycles. Table 1 shows the number of cycles before the discharge capacity is reduced to 80% of the initial discharge capacity in the first cycle. The average of the specific discharge capacity remaining in Cycles 297 to 299 is also shown in Table 2.

In various embodiments of the lithium ion battery of the present invention, the dopant metal and the fluorinated solvent pair are selected from the group consisting of (i) the dopant metal (Al, Cr, Fe, Ga, Zn, Co, Zr, Mg, V, and Cu) in any of a variety of different combinations of any of the individual members of such a whole group, any subgroup of any size taken from the entire group of doped metals (ii) any one or more of all members of the entire group of fluorinated solvents of formula (IIA), (IIB) or (III) disclosed herein, In any of a variety of different combinations of individual members of the fluorinated solvent, any subgroup of any size taken from the entire group of such fluorinated solvents, or as a single member, Taekdoem may be formed from a. Subgroups of members of the group of dopant metals or groups of fluorinated solvents may be formed by excluding any one or more members from each whole group as described above. As a result, the dopant metal or fluorinated solvent (or a pair thereof) can be any subgroup of any size that can be formed from the entire group from all the various different combinations of the individual members of the group as described in the list , But may also be made in the absence of members excluded from the total group to form a subgroup. Furthermore, the subgroups formed by excluding the various members from the entire group of the list can be individual members of the whole group, so that the dopant metal or fluorinated solvent (or a pair thereof) Can be selected in the absence of members.

The compounds of formula (IIA), (IIB) and (III) shown herein may be used in any of the following ways: (1) for one of the variable radicals, substituents or numerical coefficients , And (2) the same selection from within a defined range, in turn, for each remaining variable radical, substituent, or numerical coefficient (while the others remain constant) &Lt; / RTI &gt; each of the separate fluorinated compounds. In addition to the selection made within the range specified for any one of the variable radicals, substituents or numerical coefficients of the members of the family described in the scope, A plurality of compounds can be described by selecting fewer members than they are. (I) a single member of the entire group described in the scope, or (ii) a member selected from the group consisting of more than one of the entire group For a subgroup that includes fewer than all members, the member (s) selected is selected by excluding member (s) in the entire group that are not selected to form the subgroup. Such compounds or compounds may be characterized by the definition of one or more variable radicals, substituents or numerical coefficients in the above case, which refers to the entire group in the range specified for that variable, The excluded member (s) are not present in the whole group.

As used herein, unless expressly stated otherwise or indicated to the contrary by the context of the present application, any embodiment of the subject matter of the present invention may be embodied in, consisting of, containing, having, consisting of, One or more features or elements in addition to those explicitly described or described may be present in the embodiments. However, alternative embodiments of the subject matter of the present invention may be described or illustrated as consisting essentially of certain features or elements, in which the features or features that significantly change the operating principle or distinctive features of the embodiment Element does not exist in the embodiment. Additional alternative embodiments of the subject matter of the present invention may be described or illustrated as consisting of certain features or elements, but in this embodiment or in its fictitious variations only features or elements specifically described or described exist.

Where a range of numerical values is referred to or established herein, the range includes all the individual integers and fractions within its endpoints and ranges thereof, and also includes numerals, Each of the narrower ranges therein formed by all possible various combinations of endpoints and integers and fractions therein as if each of these narrower ranges were explicitly mentioned. Where a range of numerical values is referred to herein as being larger than a stated value, the range is nonetheless non-limiting, and the range is not limited by the value operable within the context of the present invention described herein The boundary is formed. When a range of numerical values is referred to herein as being below a stated value, the range is nonetheless bounded at its lower limit by a non-zero value.

In this specification, unless expressly stated otherwise or indicated to the contrary in the context of use,

(a) the list of compounds, monomers, oligomers, polymers and / or other chemicals includes derivatives of members of the list, and also includes any combination of two or more of each member and / or any of its respective derivatives;

(b) the amounts, sizes, ranges, formulations, parameters and other quantities and characteristics mentioned herein are not necessarily to be precise when specifically modified by the term " about ", and also include tolerances, conversion factors, rounding, a measurement error, etc., and the inclusion of values outside thereof having functional equivalents and / or operability equivalents with those described in the context of the present invention, are approximated and / May be larger or smaller).

Claims (21)

(a) a housing;
(b) an anode and a cathode disposed in the housing and in conductive contact with each other, wherein the cathode is a manganese cathode comprising a lithium-containing manganese composite oxide having a spinel structure as an active material, and the lithium- The following formula:
Li _z Mn _1.5 Ni _x M _y O _4-d
Wherein M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga, Zn, Co, Nb, Mo, Ti, Zr, Mg,
0.38 < x < 0.5,
0 < y &lt; 0.12,
0? D? 0.3,
0.00 &lt; z &lt; = 1.1 and z varies with the release and absorption of lithium ions and electrons during charging and discharging);
(c) a non-aqueous electrolyte composition disposed within the housing and providing an ionic conduction path between the anode and the cathode, wherein the non-aqueous electrolyte composition comprises at least one electrolyte salt and at least one fluorinated non-cyclic carboxylic acid ester and And / or at least one fluorinated acyclic carbonate;
(d) a lithium ion battery comprising a porous separator between the anode and the cathode. The method according to claim 1,
M is at least one metal selected from the group consisting of Al, Cr, Fe, Ga and Zn,
0.4 < x < 0.5,
0 &lt; y &lt; 0.1,
z = 1,
Lithium-ion battery with d = 0. The method of claim 1 wherein the fluorinated non-cyclic carboxylic acid ester is _{CH 3 C (O) OCH 2} CF 2 H, CH 3 C (O) OCH 2 CF 3, and _{CH 3 C (O) OCH 2} CF 2 &Lt; _{RTI ID = 0.0} &gt; CF2H. &Lt; / _RTI &gt; The method of claim 1 wherein the fluorinated non-cyclic carbonate is _{CH 3 OC (O) OCH 2} CF 2 H, CH 3 OC (O) OCH 2 CF 3, and _{CH 3 OC (O) OCH 2} CF 2 CF Lt; RTI ID = 0.0 &gt; ₂ &lt; / RTI &gt; The lithium ion battery according to claim 1, wherein M in the formula (b) includes Fe. The method of claim 3 wherein the fluorinated non-cyclic carboxylic acid ester is a lithium ion battery comprising a _{CH 3 CO 2 CH 2 CF 2} H. The nonaqueous electrolyte composition according to claim 1, wherein the non-aqueous electrolyte composition (c) is a solvent mixture comprising a fluorinated non-cyclic carboxylic acid ester and / or a fluorinated non-cyclic carbonate and at least one co- A lithium-ion battery that includes: 8. The lithium ion battery of claim 7, wherein the solvent mixture comprises from about 50% to about 80% by weight of the fluorinated non-cyclic carboxylic acid ester and / or the fluorinated non-cyclic carbonate to the solvent mixture. The lithium ion battery of claim 7, wherein the solvent mixture comprises from about 65% to about 75% by weight of the fluorinated non-cyclic carboxylic acid ester and / or the fluorinated non-cyclic carbonate to the solvent mixture. 8. The lithium ion battery of claim 7, wherein the co-solvent comprises ethylene carbonate. The method of claim 7, wherein the solvent mixture _{CH 3 CO 2 CH 2 CF 2} H , and a lithium-ion battery that includes ethylene carbonate. 12. The method of claim _{11, CH 3 CO 2 CH 2 CF} 2 H is a lithium ion battery which comprises from about 50% to about 80% by weight of the solvent mixture. 12. The method of claim _{11, CH 3 CO 2 CH 2 CF} 2 H is a lithium ion battery which comprises from about 65% to about 75% by weight of the solvent mixture. The nonaqueous electrolyte composition according to claim 1, wherein the non-aqueous electrolyte composition (c) is at least one selected from the group consisting of fluoroethylene carbonate and derivatives thereof, ethylene sulfate and derivatives thereof, vinylethylene carbonate and derivatives thereof, vinylene carbonate and derivatives thereof, An anhydride and a derivative thereof, and an additive selected from the group consisting of vinyl acetate. The lithium ion battery of claim 1, wherein the non-aqueous electrolyte composition (c) further comprises fluoroethylene carbonate. The fluorinated non-cyclic carboxylic acid ester according to claim 1,
R ^{1 -} C (O) O - R ²
(Wherein, R ¹ is _{CH 3, CH 2 CH 3,} CH 2 CH 2 CH 3, CH (CH 3) 2, CF 3, CF 2 H, CFH 2, CF 2 R 3, CFHR 3, and CH ₂ R ^f , R ² is independently selected from the group consisting of CH ₃ , CH ₂ CH ₃ , CH ₂ CH ₂ CH ₃ , CH (CH ₃ ) ₂ , and CH ₂ R ^f ; R ³ is selected from the group consisting of C ₁ -C ₃ alkyl group optionally substituted with at least one fluorine, R ^f is a C ₁ -C ₃ alkyl group substituted with at least one fluorine, at least one of R ¹ or R ² is at least one fluorine and containing; in the case where R ¹ is CF ^₂ H, R ₂ is represented by not a CH _3),
The fluorinated acyclic carbonates have the following structural formula:
R ^{4 -} OC (O) O - R ⁵
(Wherein, R ⁴ and R ⁵ are independently _{CH 3, CH 2 CH 3,} CH 2 CH 2 CH 3, CH (CH 3) is selected from the group consisting of _2, and CH ₂ R ^f; R ^f is at least one of the fluorine-substituted with C ₁ to C ₃ alkyl group and; R ⁴ or R ⁵ at least one of a lithium ion battery represented by the box containing at least one fluorine). The electrolyte salt according to claim 1, wherein the electrolyte salt in the non-aqueous electrolyte composition (c)
Lithium hexafluorophosphate,
Li PF ₃ (CF ₂ CF ₃ ) ₃ ,
Lithium bis (trifluoromethanesulfonyl) imide,
Lithium bis (perfluoroethanesulfonyl) imide,
Lithium (fluorosulfonyl) (nonafluorobutanesulfonyl) imide,
Lithium bis (fluorosulfonyl) imide,
Lithium tetrafluoroborate,
Lithium perchlorate,
Lithium hexafluoroarsenate, lithium hexafluoroarsenate,
Lithium trifluoromethane sulfonate,
Lithium tris (trifluoromethanesulfonyl) methide,
Lithium bis (oxalato) borate,
Lithium difluoro (oxalato) borate,
Li ₂ B ₁₂ F _12-x H _x where x is 0 to 8, and
A lithium ion battery selected from one or more members of the group consisting of a mixture of lithium fluoride and anion acceptor. 18. The lithium ion battery of claim 17, wherein the electrolyte salt comprises lithium hexafluorophosphate. The lithium ion battery according to claim 1, wherein the anode comprises lithium titanate or graphite as an active material. An electronically powered or assisted device comprising a lithium ion battery according to claim 1.  21. An electronic feed or auxiliary device as claimed in claim 20, which is manufactured as a transport device, a computer, a communication device, a camera, a radio, or a power tool.

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